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Herein, we report the synthesis of three O\n                    <jats:sub>2<\/jats:sub>\n                    SSe isomers from photoreaction between hydrogen selenide (H\n                    <jats:sub>2<\/jats:sub>\n                    Se) and sulfur dioxide (SO\n                    <jats:sub>2<\/jats:sub>\n                    ) via the intermediacy of selenosulfurous acid (HSeS(O)OH). Specifically, photoexcitation of the chalcogen\u2010bonded (Se\u2022\u2022\u2022S) molecular complex between H\n                    <jats:sub>2<\/jats:sub>\n                    Se and SO\n                    <jats:sub>2<\/jats:sub>\n                    at 310\u00a0nm in an Ar\u2010matrix at 10 K yields HSeS(O)OH as an elusive heavy analogue of sulfurous acid (H\n                    <jats:sub>2<\/jats:sub>\n                    SO\n                    <jats:sub>3<\/jats:sub>\n                    ). Subsequent photolysis of the matrix\u2010isolated HSeS(O)OH at 254\u00a0nm results in dehydration (\u2192 H\n                    <jats:sub>2<\/jats:sub>\n                    O + OSSe) and also dehydrogenation (\u2192 H\n                    <jats:sub>2<\/jats:sub>\n                    +\n                    <jats:italic>cis<\/jats:italic>\n                    \/\n                    <jats:italic>trans<\/jats:italic>\n                    \u2010OSSeO) reactions. Further photoexcitation of\n                    <jats:italic>cis<\/jats:italic>\n                    \/\n                    <jats:italic>trans<\/jats:italic>\n                    \u2010OSSeO causes rearrangement to\n                    <jats:italic>cyc<\/jats:italic>\n                    \u2010OS(= O)Se alongside dissociation to Se\u2022\u2022\u2022SO\n                    <jats:sub>2<\/jats:sub>\n                    . Characterization of HSeS(O)OH and the O\n                    <jats:sub>2<\/jats:sub>\n                    SSe isomers with matrix\u2010isolation IR and UV\u2010vis spectroscopy is supported by\n                    <jats:sup>18<\/jats:sup>\n                    O\u2010isotope labeling experiments and high\u2010level quantum chemical calculations. This work advances the fundamental knowledge on chalcogen chemistry, and it also helps in understanding the atmospheric photochemistry of H\n                    <jats:sub>2<\/jats:sub>\n                    Se in the global selenium cycle.\n                  <\/jats:p>","DOI":"10.1002\/anie.3323932","type":"journal-article","created":{"date-parts":[[2026,8,12]],"date-time":"2026-08-12T16:14:51Z","timestamp":1786551291000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Photochemistry of the Hydrogen Selenide\u2010Sulfur Dioxide Complex: Formation of Selenosulfurous Acid and the Dehydrogenated Polyinterchalcogen Compounds"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0009-0006-8021-8115","authenticated-orcid":false,"given":"Mengqi","family":"Luan","sequence":"first","affiliation":[{"name":"Department of Chemistry Advanced Institute of Future Energy Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials State Key Laboratory of Porous Materials For Separation and Conversion Fudan University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0002-4659-3975","authenticated-orcid":false,"given":"Junjie","family":"Jiang","sequence":"additional","affiliation":[{"name":"Department of Chemistry Advanced Institute of Future Energy Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials State Key Laboratory of Porous Materials For Separation and Conversion Fudan University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6258-7191","authenticated-orcid":false,"given":"Tarek","family":"Trabelsi","sequence":"additional","affiliation":[{"name":"Department of Earth and Environment Science University of Pennsylvania  Philadelphia USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guorui","family":"Zhang","sequence":"additional","affiliation":[{"name":"Department of Chemistry Advanced Institute of Future Energy Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials State Key Laboratory of Porous Materials For Separation and Conversion Fudan University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qi","family":"Yu","sequence":"additional","affiliation":[{"name":"Department of Chemistry Advanced Institute of Future Energy Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials State Key Laboratory of Porous Materials For Separation and Conversion Fudan University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5461-1486","authenticated-orcid":false,"given":"Joseph S.","family":"Francisco","sequence":"additional","affiliation":[{"name":"Department of Earth and Environment Science University of Pennsylvania  Philadelphia USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4611-2094","authenticated-orcid":false,"given":"Xiaoqing","family":"Zeng","sequence":"additional","affiliation":[{"name":"Department of Chemistry Advanced Institute of Future Energy Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials State Key Laboratory of Porous Materials For Separation and Conversion Fudan University  Shanghai 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